Hydrocarbon fuels stabilized against sediment



3,056,666 HYDROCARBON FUELS STABILIZED AGAINST SEDMENT Fred B. Frschl, Springfield, and Dorothy R. Bove, Roselle,

NJ., assrgnors to R550 Research and Engineering Company, a corporation of Delaware N Drawing. Filed Dec. 23, 1957, Ser. No. 704,313 7 Claims. (Cl. 44-66) This invention concerns the prevention of sediment 1n hydrocarbon fuels during storage by incorporating addrtron agents therein. These agents inhibit degradation of the fuels, and at the same time serve to disperse any sedrment producing materials that may have formed in the fuels. The addition agents employed in practicing this invention are certain organic derivatives of titanium.

The hydrocarbon fuels with which this invention is particularly concerned broadly comprise petroleum distillates that are commonly employed in various burner sys tems, as fuels for diesel engines, as aviation turbine fuels, and as domestic or industrial heating oils. These fuels may be generally characterized as those that consist of a major proportion of hydrocarbons boiling in the range of from about 150 F. to about 750 F., and particularly those boiling between 300 F. and 650 F. It is common practice to incorporate cracked hydrocarbon stocks in such fuels, and this practice aggravates the tendency of the fuels to form sediment on storage. It has been found that if percent or more of a fuel composition comprises cracked stocks, the formation of sludge or sediment during storage may be markedly increased, leading to the plugging or fouling of oil lines, filters and burner nozles. In the storage of such fuel compositions there is also a problem of rusting of iron tanks and pipes with which they come into contact, particularly when water is present and tends to be entrained with the oil.

It is a primary object of this invention to improve the stability of petroleum hydrocarbon fuels against the formation and precipitation of sediment during storage.

In accordance with the present invention the sediment forming tendencies of hydrocarbon fuels, and particularly heating oils, can be markedly reduced by incorporating minor proportions of the order of about 0.001 to about 0.09% by weight, and preferably of the order of about 0.005 to 0.05% by weight, of certain organic derivatives of titanium. This treatment also serves to reduce the rusting of ferrous metals during storage of the oils; because these titanium derivatives apparently decrease the tendency for the oils to entrain water. These derivatives are selected from the group consisting of glycol titanates, hydroxy titanium monoacylates of fatty acids and alkoxy titanium monoacylates of fatty acids. The oleates and stearates are typical acylates, e.g. hydroxy titanium mono oleate, hydroxy titanium mono stearate, alkoxy titanium mono oleate and alkoxy titanium mono stearate. The acylates are preferred because they are more effective at any given concentrations.

The organic derivatives invention may be derived titanium alkyl esters or partial appropriate fatty acid or glycol. tives may be prepared by reaction of the appropriate glycol, such as 2-ethyl-heXane-1,3-diol, 2,4,6-triethyl decane-l,3-diol, or 2-methyl-l,3-pentane diol, for example, with a titanium tetrahalide such as the tetrachloride or tetrabromide.

The acylates may be prepared by reaction of the titanium esters with the appropriate amount of the desired fatty acid. Thus, to prepare tri isopropoxy titanium mono oleate, one mole of oleic acid may be added to one mole of isopropyl titanate at 77 F. with constant stirring. Re-

of titanium employed in this from titanium tetrahalides or esters by reaction with the Thus the glycol deriva- 3,562,066 Patented Get. 2, 1962 ine action is immediate and the temperature quickly F.

where R is an aliphatic radical having from about 3 to 15, and preferably from 6 to 12, carbon atoms. It is, of course, possible for both hydroxyl groups of one glycol to react with two of the acidic groups of titanic acid.

Thus, the more probable formulae for the glycol titanates are rises to for the monoglycol or diglycol titanates, respectively, where R is the aliphatic radical of the glycol as heretofore stated.

Alkoxy glycol titanates are also contemplated, represented by the formula where R is the aliphatic radical of the glycol as heretofore stated and R is an aliphatic radical of from 3 to 12 carbon atoms, e.g. dibutoxy di (hexylene glycol) titanate.

The titanium organic acylates which are the preferred addition agents of the present invention are derivatives of titanium in the +4 state of an ortho titanic acid and are ortho-titanates having the typical formula:

(RO') -Ti-OOC-R' They may also be characterized by the general formula:

R0 '1L1-O ("J-16.

A R x where R is either hydrogen or an aliphatic group of from 1 to 20 carbon atoms, R is a fatty acid radical of from 12 to 20 carbon atoms, e.g. an oleic acid or stearic acid residue and x is an integer from 1 to 4.

It is of course to be understood that the above formulas are merely illustrative of the structures that the additives of this invention may possess and that it is not intended that the present invention be limited in any manner by any theory as to their actual structure.

Specific examples of organic titanium derivatives that may be employed in the practice of this invention include hexylene glycol titanate, dodecylene glycol titanate, octylene glycol titanate, dibutoxy di (heXylene glycol) titanate, hydroxy titanium mono oleate, tri isopropoxy titanium monostearate, di hexoxy monohydroxy titanium mono oleate and tri octoxy titanium mono laurate.

Typical fuels for use in accordance with the present invention are those meeting the requirements for Grades 1 and 2 fuel oils as set forth in ASTM Specification D 396-481, diesel fuels falling within Grades 1D, 2D and 4D of ASTM Specification D975-5 IT and aviation fuels for gas turbines as covered by U.S. Military Specification MIL-F-5624C.

The following examples serve to illustrate this invention.

EXAMPLE 1 A commercial heating oil was selected for sediment tests using the oil itself as well as mixtures of the oil with various additives, as will be explained below. The oil was a blend of 50% virgin gas oil and 50% cracked gas oil from the processing of petroleum by conventional refining methods. Typical inspections of this type of fuel oil are as follows:

Gravity, A.P.I. 36.1 Color (Tag Robinson) 13 Flash, F. 134 Sulfur (percent) 0.27 Aniline point, F. 136.5 ASTM distillation:

Initial boiling point F. 316 distilled at F. 385 50% distilled at F. 463 90% distilled at F. 576 Final boiling point F. 653

To various samples of the fuel oil were added the commercially available materials set forth in Table I below. The base fuel and each of the additive blends were subjected to an emulsion test, to determine whether the additives might have the objectionable property of facilitating the emulsification or suspension of water in the oil. 300 ml. of each sample and 30 ml. of water were shaken together for 30 seconds and then allowed to settle. The base fuel and all the blends became completely demulsified and free from aqueous haze in the same settling time of one hour. Some additives of the prior art, when tested in the same way, cause the oil to remain hazy for three days.

The base fuel and each of the additive blends were also subjected to a stability test which consisted in storing the fuel oil for a period of 16 hours while maintaining the temperature at 210 F. At the end of the 16 hours the fuel oil was filtered and the amount of sediment that had been formed during the storage period was quantitatively determined. As shown by the data in Table I each of the titanium derivatives tested was very effective in stabilizing the fuel against sediment formation.

Table I INHIBITION OF CRACKED HEATING OIL AGAINST The aliphatic radical, octylene, in this di(octylene glycol) titanate was derived from 2-ethyl-hexane diol.

The blend of 0.05 wt. percent octylene glycol titanate was also stable against color degradation by heat. This was determined by measuring the amount of transmission of a beam of white light through the fuel after the test as compared to the amount transmitted by the base fuel before the test. After 16 hours at 210 F. this blend still transmitted 71% of the original amount of White light, as against 58% transmitted by the base fuel after the same treatment.

EXAMPLE 2 A sample of commercial heating oil alone and a portion of the oil containing 0.05 wt. percent of di(octylene glycol) titanate were subjected to a rusting test in which polished steel strips were immersed in mixtures of 10% water and of each of the fuels for a period of about 14 days at room temperature. The appearance of the steel strips at the end of this period was noted. The strip that had been immersed in the inhibited fuel showed no change from its original appearance, while the strip that had been immersed in a mixture of water and uninhibited fuel was covered with heavy rust.

It is to be understood that this invention is not to be limited to the specific examples herein presented. The scope of the invention is to be determined by the appended claims, and all modifications coming within that scope are contemplated in the practice of this invention.

What is claimed is:

1. A hydrocarbon fuel boiling within the range of 150 F. and 750 F. and having a Reid Vapor Pressure of not more than 3 p.s.i. at F. to which has been added a sediment inhibiting minor proportion, between about 0.001 and 0.09 percent by weight, of an organic derivative of titanium selected from the group consisting of glycol titanates derived from glycols of from 3 to 15 carbon atoms, hydroxy titanium mono acylates and alkoxy titanium mono acylates, said acylates derived from fatty acids from about 12 to 20 carbon atoms.

2. A hydrocarbon fuel boiling within the range of F. and 750 F. and having a Reid Vapor Pressure of not more than 3 p.s.i. at 100 F. to which has been added a sediment inhibiting minor proportion, between about 0.001 and about 0.09 percent by weight, of a mono acylate of an ortho titanic acid, said acylate derived from fatty acids of from about 12 to 20 carbon atoms.

3. A hydrocarbon fuel as defined by claim 1 wherein said titanium derivative comprises t'ri isopropoxy titanium mono stearate.

4. A hydrocarbon fuel as defined by claim 1 wherein said titanium derivative comprises octylene glycol titanate.

5. A hydrocarbon fuel as defined by claim 1 wherein said titanium derivative comprises hydroxy titanium mono stearate.

6. A hydrocarbon fuel as defined by claim 1 wherein said fuel have boiling points within the range of about 300 F. and 750 F. and wherein said organic derivative of titanium is employed in a concentration of from about 0.005 to 0.05 percent by weight.

7. A fuel oil containing 0.001 to 0.09 wt. percent of di(octylene glycol) titanate.

References Cited in the file of this patent UNITED STATES PATENTS 2,560,542 Bartleson et a1 June 17, 1951 2,643,262 Bostwick June 23, 1953 2,795,553 Lowe June 11, 1957 

1. A HYDROCARBON FUEL BOILING WITHIN THE RANGE OF 150*F. AND 750*F. AND HAVING A REID VAPOR PRESSURE OF NOT MORE THAN 3 P.S.I. AT 100*F. TO WHICH HAS BEEN ADDED A SEDIMENT INHIBITING MINOR PROPORTION, BETWEEN ABOUT 0.001 AND 0.09 PERCENT BY WEIGHT, OF AN ORGANIC DERIVATIVE OF TITANIUM SELECTED FROM THE GROUP CONSISTING OF GLYCOL TITANATES DERIVED FROM GLYCOLS OF FROM 3 TO 15 CARBON ATOMS, HYDROXY TITANIUM MONO ACYLATES AND ALKOXY TITANIUM MONO ACYLATES, SAID ACYLATES DERIVED FROM FATTY ACIDS FROM ABOUT 12 TO 20 CARBON ATOMS. 